1-amino-2-hydroxyalkyl mercapto-4-hydroxy anthraquinone dyestuffs



' dyeing cellulose are of excellent resistance Patented May 26, 1953HYDROXY George W. Seymour, Cumberland,

Summit, N. J nese Corporation of America,

tor S. Salvin,

' Delaware No Drawing.

Serial No.

4 Claims.

This invention relates to novel anthraquino-ne dyestuffs and relatesmore particularly to certain mercapto-anthraquinone dyestuffs ofexcellent fastness properties.

An important object of this invention is the production of improvedanthraquinone dyestuffs acetate or other organic derivative of cellulosetextile materials in desirable red shades fast to light, washing andacid-fading.

Other objects of this invention will appear from the following detaileddescription.

Various azo and anthraquinone dyestuffs dyeing cellulose acetate orother organic derivative of cellulose textile materials in desirable redshades are available. The red dyestuffs which are of azo structure arefairly satisfactory with respect to their resistance to acid-fading buttheir light fastness leaves much to be desired. On the other hand, theavailable red dyestuffs of anthraquinone structure while exhibitingexcellent light fastness are rather poor with respect to theirresistance to acid-fading. The preparation of dyestuffs which aresuitable for dyeing cellulose acetate or other organic derivative. ofcellulose textile materials in red shades resistant both to nacid-fading and to light as well as to other agencies normally having adeleterious efiect on said dyed materials constitutes a distinct advancein the art.

S PATENT OFFICE I 2,640,062 l-AMINO-Z-HYDROXYALKYL MERCAPTO- l- ANTHRAQUINONE DYE STUFFS Md., and Vicassignors to Gelaa corporation ofApplication May 7, 1947,

mercapto 4 hydroxy anthraquinone is obtained. This1-amino-2-mercaptol-hydroxy-anthraquinone dyestuffs."

We have now found that anthraquinone dyestuffs of the following generalformula:

0 NHI S-(.OH2),.X

wherein n is a whole number and X is either a hydrogen or hydroxyradical, exhibit an unusual degree of alhnity for cellulose acetate orother organic derivative of cellulose textile materials and dye suchmaterials in valuable red shades which to light, washing andacid-fading. In addition, said dyestuffs may also be employed aspigments and excellent results may be obtained when incorporated in thecellulose acetate dope or spinning solution and the latter then spun orshaped into filaments or other materials.

Our novel dyestuffs may be obtained by reactinglamino-2.4dibrom-anthraquinone with a mixture of boric acid and sulfuricacid to form l-amino-2-brom-4-hydroxy-anthraquinone, and reacting thelatter with sodium disulfide so that hours at 150 C.

intermediate may then be reacted under reflux in an alkaline medium witha chlorhydrin as, for example, ethylene chlorhydrin, 1,3-propylenechlorhydrin, lA-butylene chlorhydrin, l-8-0ctamethylene chlorhydrin or1,12-dodecamethylene chlorhydrin or with a suitable alkyl halide such asmethyl iodide, butyl bromide or lauryl chloride, or with dimethylsulfate, to form the desired substituted mercapto We may thus obtainanthraquinone dyestuffs such as, for example, l-amino-2-methyl mercapto4 hydroxy anthraquinone. l amino 2 hydroxyethyl mercapto 4- hydroxyanthraquinone, l amino 2 hydroxypropyl mercapto 4 hydroxy anthraquinone,1 amino 2 hydroxy-butyl mercapto 4 hydroxy anthraquinone, 1 amino 2-hydroxyoctyl mercapto 4 hydroxy anthraquinone, 1 amino 2 hydroxylaurylmercapto 4 hydroxy anthraquinone or 1 amino 2 lauryl mercapto 4 hydroxyanthraquinone. Suitable alkaline agents which may :be employed forrendering the reaction medium alkaline are, for example, sodiumhydroxide, sodium bicarbonate, magnesium hydroxide, or sodium carbonate.

In order further to illustrate our invention, but without being limitedthereto, the following examples are given:

E sample I 30 parts by weight of 1-amin0-2A-dibromanthraquinone aredissolved in 200 parts by weight of concentrated sulfuric acid and 20parts by weight of boric acid are added thereto. The solution obtainedis heated with stirring for 8 During the reaction, hydrogen bromide andsome free bromine are evolved. The reaction mixture obtained is cooled,dropped on to ice and l-amino-2-brom-4-hydroxy-anthraquinoneprecipitates out as a red solid. The latter is filtered 01f and thenwashed free of acid.

A mixture of about parts by weight of ethyl alcohol, 10 parts by weightof sulfur and 28 parts by weight of crystalline sodium sulfide areheated together until complete solution is obtained and. then 20 part byweight of l-amino-2-brom-4- hydroxy-anthraquinone are added. Thereaction mixture is maintained under reflux for 6 hours during whichtime the color changes from a wine to a violet. After heating iscompleted the reaction mixture is acidified with dilute hydrochloricacid and the 1-amino-2-mercapto-4- of 'I-amin'o- 2 nonecontaining 8parts by weight of the latter reaction mixture is held at 80 The'1-amino-2-methylmercapto-' hydroxy-anthraquinone present precipitatestogether with sulfur.

capto-4-hydroxy-anthraquinone is then refluxed with about 30 parts byweight 'ofetliylenechlor- 11 takes place r'ap'ikll'y and after one houra red suspension of I-aminmZ-hydrox yethyl-mercapto 4hydroxyeanthraguinone A yield of about 73% of theoretical based on the 1-amino- 2 -brom- 4 -hydroxy-anthreiqumo1re obtained. The dyestuif1-amino-2-hydroxyethylmercapto-4-hydroxy-anthraquinone dyescellumaterials in attractive red shades Example II by weight of analkaline solution 4 hydroxy-anthraqui- To 300 .parts "obtained. Thedyestuff l-amino-Z-methylmer- 'capto-4-hydroxy-anthraquinone dyescellulose Example III To 200 parts by weight of an alkaline solution of1-amino-2 -hydroxy-anthra'quiadded 80 parts by weight of ethyl alcoholand 20 parts by weight of lauryl chloride. The mixture is held underreflux at 85 C. for 2 hours,

'l-amino-2-lauryl mercap'to 4 hydroxy-anthraquinon'e is complete. Thedyestufi is isolated by srecrystallized from alcohol..lauryl-mercapto-4-1yclroxy-anthtaql1inone dyes cellulose acetate in red.shades. material does not noticeably change after expo- ,sure tovultra-violet .light for 50 --hibi'ts a resistance to acid-fading of-24) units'in accordance with the standard A.

.fading test.

filtration and may be The l-amino-2- The dyed acetate hours t and it ex-.Whileour invention has been more particularly described in connectionwith the dyeing of cellulose-acetate materials, textile materials havingf a basis of other organic derivatives of cellulose may be dyed with ournovel dyestuffs as well.

. invention.

Examples of other organic derivatives of cellulose are cellulose esterssuch as cellulose propionate, cellulose butyrate, celluloseacetatepropionate, cellulose acetate-butyrate as Well as celluloseethers such as ethyl cellulose and benzyl cellulose. 1

'It is to 'be understood that the foregoing detailed description isgiven merely by way of illustration and that many variations may be madewithout departing from the spirit of our Having describedour invention,what we desire to "secure by Letters Patent is:

11. arithraliuinone dyestuffs or the following general formula:

oH wherein n is a whole number.

2. The anthraquinone dyestu'tf com-prising essentially l-amino 2'-:hydroxyethyl*mercapto-4- hydroxy-anthraquinone.

.Process .for the 1 production of :anthraquinone dyestuffs of the:following :general formula:

hydrin. M V I GEORGE W. VICTOR S. SALVIN. References Cited in the file'of this patent UNITED STATES PATENTS Number Name Date 1,062,990Naw'i'asky May 27, 1913 1,710,992 Kranzlein et a1. Apr. 30, 19291,881,752 Lodge et 'ai. Oct. 11, 1932 1,964,971 Albrecht et 8.1. l July3, 1934 2,081,755 Lodge May 25, 19 37 2;1o'1;91'0 nodgeet a1. Dec. 11,193! 2,434,765 Grossmahn Jan. '20, I948 FOREIGN PATENTS Number CountryDa'te $558,433 EGreat'Britain l 1 Jan. 5, 1944 OTHER REFERENCES .Lowy etal.: Introduction to Organic Chemistry, 6th .edition, ;pages.'2l3-14,1946, John Wiley iii-Sons, New York.

1. THE ANTHRAQUINONE DYESTUFFS OF THE FOLLOWING GENERAL FORMULA: